US6210764B1 - Film with substrate layer containing antiblocking agent - Google Patents

Film with substrate layer containing antiblocking agent Download PDF

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Publication number
US6210764B1
US6210764B1 US08/706,993 US70699396A US6210764B1 US 6210764 B1 US6210764 B1 US 6210764B1 US 70699396 A US70699396 A US 70699396A US 6210764 B1 US6210764 B1 US 6210764B1
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ethylene
film
antiblocking agent
packaged product
copolymer
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Gary J. Hayes
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Cryovac LLC
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Cryovac LLC
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Priority to US08/706,993 priority Critical patent/US6210764B1/en
Assigned to W.R. GRACE & CO- CON reassignment W.R. GRACE & CO- CON ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HAYES, GARY J.
Priority to CA002213362A priority patent/CA2213362A1/en
Priority to BR9704559A priority patent/BR9704559A/pt
Priority to ES97306599T priority patent/ES2166050T3/es
Priority to AT97306599T priority patent/ATE209104T1/de
Priority to PT97306599T priority patent/PT826491E/pt
Priority to EP97306599A priority patent/EP0826491B1/en
Priority to DE69708417T priority patent/DE69708417T2/de
Priority to ARP970103956A priority patent/AR009359A1/es
Assigned to CRYOVAC, INC. reassignment CRYOVAC, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: W.R. GRACE & CO.-CONN.
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/91—Product with molecular orientation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1328—Shrinkable or shrunk [e.g., due to heat, solvent, volatile agent, restraint removal, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24372—Particulate matter
    • Y10T428/2438—Coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

  • the present invention relates generally to multilayer films, and particularly to packaging films.
  • the present invention also relates to packages, especially packages having one or more seals, as well as packaged products.
  • antiblocking agents such as particulate silica
  • these antiblocking agents offer two advantages. First, they help to prevent the film from sticking or blocking to itself when the film is rolled up on itself during the manufacture of the film. Second, the antiblock offers a beneficial “roller bearing” effect when the film is run across metal parts in typical commercial packaging equipment. An example of such equipment is a DoboyTM horizontal form/fill/seal machine.
  • Fatty acid amides sometimes referred to as slip agents, are often also included in the film, in order to provide the film with a desirable film-to-film coefficient of friction, so that packaged products slide freely when in contact with one another. This is desired in order to facilitate alignment of packaged products for the bulk packaging thereof, for example in boxes, as well as providing a desired low film-to-equipment coefficient of friction.
  • Abrasion of machine parts can also result from the use of films containing antiblocking agents in the surface layer, akin to the use of sandpaper on a metal surface.
  • the present invention relates to a multilayer film comprising a first outer layer comprising a polymeric material; a second outer layer comprising a polymeric material; and a substrate layer, disposed between the first and second outer layers, comprising a polymeric material and an antiblocking agent.
  • the present invention relates to a multilayer film comprising a first outer layer comprising a polymeric material; a second outer layer comprising a polymeric material; a core layer, disposed between the first and second outer layers, comprising a polymeric material; and a first substrate layer, disposed between the core layer and the first outer layer, comprising a polymeric material and an antiblocking agent.
  • one or more additional substrate or internal layers can be included in the film structure of the invention.
  • FIGS. 1 to 4 schematically illustrate cross-sectional views of multilayer films according to the present invention.
  • film is used in a generic sense to include a web, film, sheet, laminate, or the like, whether coextruded, extrusion laminated, extrusion coated, conventionally laminated, or otherwise produced by any other process.
  • antiblocking agent refers to an additive that is incorporated into a film to prevent the surface of a film from sticking to itself or other surfaces. These are organic or inorganic materials that, when included in a layer of a film, affect the final film surface topography on at least one outside surface of the film. It has been discovered that antiblocking agents can be incorporated in the substrate layer of a multilayer film, yet still create protrusions or roughness on at least one of the outer surfaces of the film. This occurs because of the presence of the antiblocking agent, which results in a deformation of the adjacent outer layer, causing the polymer of the outer layer to be displaced in portions of the outer layer near the antiblocking material.
  • the phrases “seal layer”, “sealing layer”, “heat seal layer”, “sealant layer”, and the like refer to an outer film layer, or layers, involved in the sealing of the film to itself, another film layer of the same or another film, and/or another article which is not a film. Sealing can be performed by many means, such as using a hot wire, hot knife, heated bar, hot air, infrared radiation, ultrasonic sealing, etc.
  • oriented refers to a polymer-containing material which has been stretched at an elevated temperature (the orientation temperature), followed by being “set” in the stretched configuration by cooling the material while substantially retaining the stretched dimensions. Upon subsequently heating unrestrained, unannealed, oriented polymer-containing material to its orientation temperature, heat shrinkage is produced.
  • the term “monomer” refers to a relatively simple compound, usually containing carbon and of low molecular weight, which can react to form a polymer by combining with itself or with other similar molecules or compounds.
  • the term “comonomer” refers to a monomer which is copolymerized with at least one different monomer in a copolymerization reaction, the result of which is a copolymer.
  • polymer refers to the product of a polymerization reaction, and is inclusive of homopolymers, copolymers, terpolymers, etc.
  • the layers of a film can consist essentially of a single polymer, or can have still additional polymers together therewith, i.e., blended therewith.
  • homopolymer is used with reference to a polymer resulting from the polymerization of a single monomer, i.e., a polymer consisting essentially of a single type of repeating unit.
  • copolymer refers to polymers formed by the polymerization reaction of at least two different monomers.
  • copolymer includes the copolymerization reaction product of ethylene and an alpha-olefin, such as 1-hexene.
  • copolymer is also inclusive of, for example, the copolymerization of a mixture of ethylene, propylene, 1-hexene, and 1-octene.
  • polymerization is inclusive of homopolymerizations, copolymerizations, terpolymerizations, etc., and includes all types of copolymerizations such as random, graft, block, etc.
  • copolymerization refers to the simultaneous polymerization of two or more monomers.
  • a copolymer identified in terms of a plurality of monomers refers to a copolymer in which either monomer may copolymerize in a higher weight or molar percent than the other monomer or monomers.
  • copolymers are identified, i.e., named, in terms of the monomers from which the copolymers are produced.
  • the phrase “propylene/ethylene copolymer” refers to a copolymer produced by the copolymerization of both propylene and ethylene, with or without additional comonomer(s).
  • ethylene alpha-olefin copolymer is the equivalent of “ethylene/alpha-olefin copolymer.”
  • heterogeneous polymer refers to polymerization reaction products of relatively wide variation in molecular weight and relatively wide variation in composition distribution, i.e., typical polymers prepared, for example, using conventional Ziegler-Natta catalysts. Heterogeneous polymers are useful in various layers of the film used in the present invention. Although there are a few exceptions (such as TAFMERTM linear homogeneous ethylene/alpha-olefin copolymers produced by Mitsui Petrochemical Corporation, using Ziegler-Natta catalysts), heterogeneous polymers typically contain a relatively wide variety of chain lengths and comonomer percentages.
  • heterogeneous catalyst refers to a catalyst suitable for use in the polymerization of heterogeneous polymers, as defined above.
  • Heterogeneous catalysts are comprised of several kinds of active sites which differ in Lewis acidity and steric environment.
  • Ziegler-Natta catalysts are heterogeneous catalysts. Examples of Ziegler-Natta heterogeneous systems include metal halides activated by an organometallic co-catalyst, such as titanium chloride, optionally containing magnesium chloride, complexed to trialkyl aluminum, as is disclosed in patents such as U.S. Pat. No. 4,302,565, to GOEKE, et. al., and U.S. Pat. No. 4,302,566, to KAROL, et. al., both of which are hereby incorporated, in their entireties, by reference thereto.
  • homogeneous polymer refers to polymerization reaction products of relatively narrow molecular weight distribution and relatively narrow composition distribution. Homogeneous polymers are useful in various layers of the multilayer film used in the present invention. Homogeneous polymers are structurally different from heterogeneous polymers, in that homogeneous polymers exhibit a relatively even sequencing of comonomers within a chain, a mirroring of sequence distribution in all chains, and a similarity of length of all chains, i.e., a narrower molecular weight distribution. Furthermore, homogeneous polymers are typically prepared using metallocene, or other single-site type catalysts, rather than using Ziegler Natta catalysts.
  • homogeneous ethylene/alpha-olefin copolymers may be characterized by one or more methods known to those of skill in the art, such as molecular weight distribution (M w /M n ), composition distribution breadth index (CDBI), and narrow melting point range and single melt point behavior.
  • M w /M n molecular weight distribution
  • CDBI composition distribution breadth index
  • the molecular weight distribution (M w /M n ) also known as polydispersity, may be determined by gel permeation chromatography.
  • the homogeneous ethylene/alpha-olefin copolymers useful in this invention generally have (M w /M n ) of less than 2.7; preferably from about 1.9 to 2.5; more preferably, from about 1.9 to 2.3.
  • composition distribution breadth index (CDBI) of such homogeneous ethylene/alpha-olefin copolymers will generally be greater than about 70 percent.
  • the CDBI is defined as the weight percent of the copolymer molecules having a comonomer content within 50 percent (i.e., plus or minus 50%) of the median total molar comonomer content.
  • the CDBI of linear polyethylene, which does not contain a comonomer, is defined to be 100%.
  • the Composition Distribution Breadth Index (CDBI) is determined via the technique of Temperature Rising Elution Fractionation (TREF).
  • CDBI determination clearly distinguishes the homogeneous copolymers used in the present invention (narrow composition distribution as assessed by CDBI values generally above 70%) from VLDPEs available commercially which generally have a broad composition distribution as assessed by CDBI values generally less than 55%.
  • the CDBI of a copolymer is readily calculated from data obtained from techniques known in the art, such as, for example, TREF as described, for example, in Wild et. al., J. Poly. Sci. Poly. Phys. Ed., Vol. 20, p.441 (1982).
  • the homogeneous ethylene/alpha-olefin copolymers have a CDBI greater than about 70%, i.e., a CDBI of from about 70% to 99%.
  • the homogeneous ethylene/alpha-olefin copolymers in the multilayer films of the present invention also exhibit a relatively narrow melting point range, in comparison with “heterogeneous copolymers”, i.e., polymers having a CDBI of less than 55%.
  • a homogeneous ethylene/alpha-olefin copolymer can, in general, be prepared by the copolymerization of ethylene and any one or more alpha-olefin.
  • the alpha-olefin is a C 3 -C 20 alpha-monoolefin, more preferably, a C 4 -C 12 alpha-monoolefin, still more preferably, a C 4 -C 8 alpha-monoolefin.
  • the alpha-olefin comprises at least one member selected from the group consisting of butene-1, hexene-1, and octene-1, i.e., 1-butene, 1-hexene, and 1-octene, respectively. Most preferably, the alpha-olefin comprises octene-1, and/or a blend of hexene-1 and butene-1.
  • homogeneous catalyst refers to a catalyst suitable for use in the polymerization of homogeneous polymers, as defined above.
  • homogeneous catalysts are also referred to as “single site catalysts”, due to the fact that such catalysts typically have only one type of catalytic site, which is believed to be the basis for the homogeneity of the polymers resulting from the polymerization.
  • polyolefin refers to any polymerized olefin, which can be linear, branched, cyclic, aliphatic, aromatic, substituted, or unsubstituted. More specifically, included in the term polyolefin are homopolymers of olefin, copolymers of olefin, copolymers of an olefin and a non-olefinic comonomer copolymerizable with the olefin, such as vinyl monomers, styrenic monomers, modified polymers thereof, and the like.
  • polyethylene homopolymer polypropylene homopolymer, polybutene, ethylene/alpha-olefin copolymer, propylene/alpha-olefin copolymer, butene/alpha-olefin copolymer, ethylene/vinyl acetate copolymer, ethylene/ethyl acrylate copolymer, ethylene/butyl acrylate copolymer, ethylene/methyl acrylate copolymer, ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, modified polyolefin resin, ionomer resin, polymethylpentene, olefin/styrene copolymers, etc.
  • Modified polyolefin resin is inclusive of modified polymer prepared by copolymerizing the homopolymer of the olefin or copolymer thereof with an unsaturated carboxylic acid, e.g., maleic acid, fumaric acid or the like, or a derivative thereof such as the anhydride, ester or metal salt or the like. It could also be obtained by incorporating into the olefin homopolymer or copolymer, an unsaturated carboxylic acid, e.g., maleic acid, fumaric acid or the like, or a derivative thereof such as the anhydride, ester or metal salt or the like.
  • an unsaturated carboxylic acid e.g., maleic acid, fumaric acid or the like
  • a derivative thereof such as the anhydride, ester or metal salt or the like.
  • identifying polymers such as “polyamide”, “polyester”, “polyurethane”, etc. are inclusive of not only polymers comprising repeating units derived from monomers known to polymerize to form a polymer of the named type, but are also inclusive of comonomers, derivatives, etc. which can copolymerize with monomers known to polymerize to produce the named polymer.
  • polyamide encompasses both polymers comprising repeating units derived from monomers, such as caprolactam, which polymerize to form a polyamide, as well as copolymers derived from the copolymerization of caprolactam with a comonomer which when polymerized alone does not result in the formation of a polyamide.
  • terms identifying polymers are also inclusive of mixtures, blends, etc. of such polymers with other polymers of a different type. More preferably, however, the polyolefin is the polymerization product of one or more unsubstituted olefins, the polyamide is the polymerization product of one or more unsubstituted amides, etc.
  • ethylene alpha-olefin copolymer and “ethylene/alpha-olefin copolymer”, refer to such heterogeneous materials as linear low density polyethylene (LLDPE), and very low and ultra low density polyethylene (VLDPE and ULDPE); and homogeneous polymers such as metallocene-catalyzed EXACTTM linear homogeneous ethylene/alpha olefin copolymer resins obtainable from the Exxon Chemical Company, of Baytown, Tex., and TAFMERTM linear homogeneous ethylene/alpha-olefin copolymer resins obtainable from the Mitsui Petrochemical Corporation.
  • LLDPE linear low density polyethylene
  • VLDPE and ULDPE very low and ultra low density polyethylene
  • homogeneous polymers such as metallocene-catalyzed EXACTTM linear homogeneous ethylene/alpha olefin copolymer resins obtainable from the Exxon Chemical Company, of Baytown, Tex
  • All these materials generally include copolymers of ethylene with one or more comonomers selected from C 4 to C 10 alpha-olefin such as butene-1 (i.e., 1-butene), hexene-1, octene-1, etc. in which the molecules of the copolymers comprise long chains with relatively few side chain branches or cross-linked structures.
  • This molecular structure is to be contrasted with conventional low or medium density polyethylenes which are more highly branched than their respective counterparts.
  • the heterogeneous ethylene/alpha-olefin commonly known as LLDPE has a density usually in the range of from about 0.91 grams per cubic centimeter to about 0.94 grams per cubic centimeter.
  • ethylene/alpha-olefin copolymers such as the long chain branched homogeneous ethylene/alpha-olefin copolymers available from The Dow Chemical Company, known as AFFINITYTM resins, are also included as another type of homogeneous ethylene/alpha-olefin copolymer useful in the present invention.
  • the ethylene/alpha-olefin copolymer comprises a copolymer resulting from the copolymerization of from about 80 to 99 weight percent ethylene and from 1 to 20 weight percent alpha-olefin.
  • the ethylene/alpha-olefin copolymer comprises a copolymer resulting from the copolymerization of from about 85 to 95 weight percent ethylene and from 5 to 15 weight percent alpha-olefin.
  • substrate layer refers to any layer, of a multilayer film, having both of its principal surfaces directly adhered to another layer of the film.
  • substrate layer refers to a layer adjacent an outer layer.
  • outer layer refers to any film layer of film having less than two of its principal surfaces directly adhered to another layer of the film.
  • internal layer refers to a substrate layer.
  • the term “extrusion” is used with reference to the process of forming continuous shapes by forcing a molten plastic material through a die, followed by cooling or chemical hardening. Immediately prior to extrusion through the die, the relatively high-viscosity polymeric material is fed into a rotating screw of variable pitch, i.e., an extruder, which forces the polymeric material through the die.
  • coextrusion refers to the process of extruding two or more materials through a single die with two or more orifices arranged so that the extrudates merge and weld together into a laminar structure before chilling, i.e., quenching. Coextrusion can be employed in film blowing, free film extrusion, and extrusion coating processes.
  • machine direction refers to a direction “along the length” of the film, i.e., in the direction of the film as the film is formed during extrusion and/or coating.
  • TD transverse direction
  • free shrink refers to the percent dimensional change in a 10 cm ⁇ 10 cm specimen of film, when shrunk at 200° F., with the quantitative determination being carried out according to ASTM D 2732, as set forth in the 1990 Annual Book of ASTM Standards, Vol. 08.02, pp.368-371, which is hereby incorporated, in its entirety, by reference thereto.
  • the film according to the present invention preferably has a “total free shrink at 200° F.”, i.e., the sum of the free shrink in the machine direction, at 200° F., and the free shrink in the transverse direction, at 200° F., of from about 10 to 80 percent; more preferably, from about 15 to 70 percent; still more preferably, from about 20 to 60 percent, such as 25 to 40 percent.
  • a “total free shrink at 200° F.” i.e., the sum of the free shrink in the machine direction, at 200° F., and the free shrink in the transverse direction, at 200° F., of from about 10 to 80 percent; more preferably, from about 15 to 70 percent; still more preferably, from about 20 to 60 percent, such as 25 to 40 percent.
  • the phrase “free shrink”, as used herein, refers to total free shrink.
  • the outer film layers preferably comprise polyolefin.
  • the polyolefin comprises at least one member selected from the group consisting of polyethylene and polypropylene.
  • the polyethylene comprises at least one member selected from the group consisting of linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), linear medium density polyethylene (LMDPE), high density polyethylene (HDPE), ethylene/vinyl acetate copolymer (EVA), ethylene/butyl acrylate copolymer (EBA), and homogeneous ethylene/alpha-olefin copolymer.
  • the polypropylene comprises at least one member selected from the group consisting of propylene homopolymer, propylene/ethylene random copolymer, propylene/butene copolymer, and propylene/ethylene/butene terpolymer.
  • the propylene/ethylene random copolymer comprises ethylene mer in an amount of from about 0.5 to 30 weight percent, based on the weight of the propylene/ethylene random copolymer; more preferably, ethylene mer in an amount of from about 0.5 to 10 percent, and still more preferably, from about 2 to 6 weight percent.
  • the polypropylene may comprise syndiotactic polypropylene.
  • the outer layers may instead, or additionally, comprise homogeneous polymer, such as homogeneous ethylene/alpha-olefin copolymer.
  • a particularly preferred outer layer comprises propylene/ethylene copolymer, polybutylene, and homopolymer polypropylene.
  • Another particularly preferred outer layer comprises propylene/ethylene random copolymer and polypropylene homopolymer.
  • the outer layer may further comprise butylene homopolymer, i.e., in addition to one or more of the polyolefins described above.
  • Another preferred outer layer comprises a blend of linear low density polyethylene and ethylene/vinyl acetate copolymer. Linear medium density polyethylene can also be included.
  • the inner layer(s) of the film preferably comprises ethylene-based polymer, more preferably ethylene/alpha-olefin copolymer, including both heterogeneous ethylene/alpha-olefin copolymer and homogeneous ethylene/alpha-olefin copolymer.
  • Linear low density polyethylene (LLDPE) is a preferred heterogeneous ethylene/alpha-olefin copolymer for use in the core layer.
  • the antiblocking agent may comprise mineral-based antiblocking agent and/or synthetic-based antiblocking agent.
  • Mineral-based antiblocking agents include both silica-based agents (e.g., diatomaceous earth, quartz, and silica sand), as well as others such as kaolin, talc, feldspar, and calcium carbonate.
  • Synthetic-based antiblocking agents include synthetic silica antiblocking agents, for example gel-type synthetic silica, and precipitated-type synthetic silica.
  • the antiblocking agent comprises at least one member selected from the group consisting of silica, silicate, and glass, and preferably the antiblocking agent is in the form of approximately spherical particles.
  • the antiblocking agent is in the form of approximately spherical particles.
  • particles of irregular shape, and angular particles can be used.
  • the antiblocking agent comprises at least one member selected from the group consisting of aluminum silicate (clay), silica (silicon dioxide), sodium calcium alumino silicate, magnesium silicate (talc), and calcium silicate; more preferably, at least one member selected from the group consisting of aluminum silicate, silica, sodium calcium alumino silicate, and magnesium silicate; still more preferably, at least one member selected from the group consisting of aluminum silicate, silica, and sodium calcium alumino silicate; yet still more preferably, at least one member selected from the group consisting of aluminum silicate and silica; and yet still more preferably, aluminum silicate.
  • Preferred antiblocking agents are W-410 and JC-30. These materials are described herein.
  • the antiblocking agent can comprise an organic material such as crosslinked or uncrosslinked organic materials. Examples include polyester, EVOH (ethylene/vinyl alcohol copolymer), nylon 6, nylon 6,6, syndiotactic polystyrene, engineering resins, liquid crystalline polymers, and aromatic nylons. Selecting the appropriate antiblocking agent depends at least in part on the nature of the layer in which the antiblocking agent is present. The Vicat softening point of the organic antiblocking agent should be sufficiently higher than that of the host polymer such that the organic antiblocking agent functions as an antiblocking agent as described herein.
  • antiblocking agents have an average particle size (diameter) of from about 0.1 to 10 microns, such as 1 to 8 microns, and 2 to 6 micrometer, and are preferably present at a level of from 0.1 to 6 weight percent, such as 0.2 to 4 wt. %, and 0.3 to 3 wt. %, based on the weight of the substrate layer.
  • organosiloxane i.e., silicone oil
  • the organosiloxane preferably comprises at least one member selected from the group consisting of polydimethylsiloxane, polymethylphenylsiloxane, olefin-modified silicone, polyether (e.g., polyethylene glycol, polypropylene glycol)-modified silicone, olefin/polyether-modified silicone, epoxy-modified silicone, amino-modified silicone, alcohol-modified silicon, etc.
  • polydimethylsiloxane is preferred.
  • the organosiloxane is preferably present in the substrate layer in an amount of from about 0.1 to 1.0 weight percent based on the weight of the substrate layer, more preferably in an amount of from about 0.1 to 0.5 weight percent, still more preferably 0.16 to 0.5 weight percent, and yet still more preferably in an amount of 0.18 to 0.5 weight percent.
  • one or more of the outer layers and/or substrate layer(s) includes fatty amide, preferably in an amount of from about 0.1 to 1 percent, based on the weight of the layer; more preferably, from about 0.2 to 0.6 percent; still more preferably, from about 0.2 to 0.4 percent.
  • the fatty amide comprises at least one member selected from the group consisting of primary fatty amide, secondary fatty amide, tertiary fatty amide, fatty alkanolamide, and fatty bisamide. More specifically, the fatty amide preferably comprises at least one member selected from the group consisting of erucamide, stearamide, oleamide, behenamide, and ethylene bisstearamide.
  • Fatty amides are described in detail in Arthur L. McKenna, “Fatty Amides” (1992, Witco Chemical Corporation), which is hereby incorporated by reference thereto, in its entirety.
  • the film preferably has a film-to-film coefficient of friction of from about 0.1 to 0.9, more preferably the film has a film-to-film coefficient of friction of from about 0.1 to 0.7, still more preferably, from about 0.1 to 0.5, and yet still more preferably, from about 0.1 to 0.3.
  • the film has a total thickness of preferably less than about 20 mils, more preferably the film has a total thickness of from about 0.2 to 10 mils, still more preferably from about 0.3 to 4 mils, and yet still more preferably, from about 0.4 to 2 mils, such as 0.5 to 1 mil.
  • a Gardner Goniophotometer is capable of determining total transmission, i.e., measuring light striking at any and all angles, and the reflection or transmission of this light from any angle.
  • the film clarity can be measured using the method of ASTM D 1746, as set forth in the 1990 Annual Book of ASTM Standards, Vol. 08.02, pp.76-78, which is hereby incorporated, in its entirety, by reference thereto.
  • Haze can be measured using the method of ASTM D 1003, as is discussed below.
  • Gloss can be measured using the method of ASTM D 2457, as set forth in the 1990 Annual Book of ASTM Standards, Vol. 08.02, pp.266-269, which is hereby incorporated, in its entirety, by reference thereto.
  • Clarity refers to the optical distinctness with which an object can be seen when viewed through the sheet. Clarity may be thought of as the distinctness with which an object appears when viewed through a film. Clarity may also be described as the quality of image formation through a sheet, and depends upon the linearity of the passage of light rays through the material. Small deflections of the light, caused by the scattering centers of the material, bring about a deterioration of the image, i.e., a decrease in clarity, these deflections being much smaller than those registered in haze measurements.
  • the film of the present invention preferably has a clarity of from about 20 percent to 100 percent, more preferably the film has a clarity of from about 40 to 100 percent, still more preferably from about 60 to 100 percent, and still more preferably, from 80 to 100 percent.
  • Some of the multilayer films of the present invention are preferably irradiated to induce crosslinking.
  • the film is subjected to an energetic radiation treatment, such as corona discharge, plasma, flame, ultraviolet, X-ray, gamma ray, beta ray, and high energy electron treatment, which induce cross-linking between molecules of the irradiated material.
  • an energetic radiation treatment such as corona discharge, plasma, flame, ultraviolet, X-ray, gamma ray, beta ray, and high energy electron treatment, which induce cross-linking between molecules of the irradiated material.
  • the irradiation of polymeric films is disclosed in U.S. Pat. No.
  • BORNSTEIN et. al. discloses the use of ionizing radiation for crosslinking the polymer present in the film.
  • a suitable radiation dosage of high energy electrons preferably using an electron accelerator, with a dosage level being determined by standard dosimetry methods.
  • Other accelerators such as a Van de Graaff generator or resonating transformer may be used.
  • the radiation is not limited to electrons from an accelerator since any ionizing radiation may be used.
  • the ionizing radiation can be used to crosslink the polymers in the film.
  • the film is irradiated at a level of from 2-15 MR, more preferably 2-10 MR. As can be seen from the descriptions of preferred films for use in the present invention, the most preferred amount of radiation is dependent upon the film composition, thickness, etc., and its end use.
  • the antiblocking agent can be used in a substrate layer or layers, and optionally in one or more other layers of a wide variety of film and sheet materials. More specifically, the antiblocking agent can be used in any one or more of the substrate layers of films disclosed in: U.S. Pat. No. 4,532,189, issued Jul. 30, 1985 to W. B. Mueller; U.S. Pat. No. 4,551,380 issued Nov. 5, 1985 to J. H. Schoenberg; U.S. Pat. No. 4,724,185 issued Feb. 9, 1988 to G. P. Shah; U.S. Pat. No. 4,755,419 issued Jul. 5, 1988 to G. P. Shah; U.S. Pat. No. 5,023,143 issued Jun. 11, 1991 to M. Nelson; U.S. Pat. No. 5,298,302, issued Mar. 29, 1994 to P. R. Boice; and U.S. Pat. No. 5,482,771, issued Jan. 9, 1996 to G. P. Shah. Each of these patents is hereby incorporated by reference thereto, in its entirety
  • the present invention is especially useful in symmetrical three-layer films, and symmetrical five-layer films, each having propylene-based outer layers and at least one ethylene-based inner layer.
  • Films which can beneficially use the invention include barrier films as well as non-barrier films, irradiated as well as non-irradiated films, symmetrical and non-symmetrical films, films containing adhesive layers, and films containing one or more interior functional layers.
  • FIG. 1 illustrates a cross-sectional view of a preferred, oriented three-layer film 10 .
  • First layer 12 is an outer film layer which can serve as a sealing layer, and either an abuse layer or a product contact layer.
  • Second layer 14 is a substrate film layer which can serve as a bulk layer.
  • Third layer 16 is also an outer layer, and can also serves as a sealing layer as well as an abuse layer or a product contact layer.
  • first layer 12 and third layer 16 are of substantially identical chemical composition and substantially identical thickness, so that multilayer film 10 has a substantially symmetrical cross-section.
  • Outer layers 12 and 16 each comprise a polymeric material
  • substrate layer 14 comprises a polymeric material and an antiblocking agent 17 .
  • FIG. 2 shows a film 20 like that of FIG. 1, but including five layers.
  • the antiblocking agent 27 is present in two substrate layers 24 and 28 , flanked respectively by the central core layer 26 and outer layers 22 and 30 .
  • FIG. 3 shows an unoriented five layer film 32 ;
  • FIG. 4 shows the same film after orientation, and similar to the film of FIG. 2.
  • a preferred method for making the film of the present invention is as set forth in U.S. Pat. Nos. 4,532,189, and 5,298,302, both patents incorporated by reference herein in their entirety.
  • Individual resin components or blends which are to form each layer are fed to extruders. Inside the extruders, the polymer beads are forwarded, melted, and degassed, following which the resulting bubble-free melt is forwarded into a die head, and extruded through an annular die, resulting in a tape, in the form of a tubing, the tape preferably having a thickness of about 5 to 50 mils.
  • the tape is then rapidly cooled to room temperature (optionally by water spray from a cooling ring) and thereafter collapsed by pinch rolls.
  • the tape can be irradiated, the tape is preferably not irradiated because polypropylene, a preferred polymer for use in the film, degrades with radiation.
  • the film comprises only polymers which do not degrade upon irradiation, it may be preferred to irradiate the tape.
  • the tape is then heated to a preferred orientation temperature by using a radiant heating means (e.g., infrared radiation) and/or conductive heating means (e.g., superheated steam) and/or convective heating means (e.g., heated air).
  • a preferred orientation temperature is from about 75° C.
  • the heated tape is directed through pinch rolls, following which the heated tape is inflated, resulting in a trapped bubble.
  • internal air pressure stretches the heated tape in an amount of from about 1.5 ⁇ to 8 ⁇ in the transverse direction (preferably from about 3 ⁇ to 7 ⁇ ).
  • roller speed differential i.e., between the first and second set of pinch rolls, simultaneously draws the heated tape in an amount of from about 1.5 ⁇ to 8 ⁇ in the machine direction (preferably from about 3 ⁇ to 7 ⁇ ).
  • a biaxially oriented film 20 is formed.
  • the biaxially oriented film is then rapidly cooled using chilled air, in order to maintain the degree of biaxial orientation.
  • the biaxially oriented film is wound onto a take-up roll.
  • PEC EscoreneTM PD 9302 propylene/ethylene random copolymer having 3.3% by weight of ethylene, obtained from the Exxon Chemical Americas, of Houston, Tex.
  • PB Duraflex 0 300 TM polybutylene homopolymer having a density of 0.915 g/cc, obtained from the Shell Chemical Company, of Hahnville, La.
  • PP PD 4062E-7 TM polypropylene homopolymer having a density of 0.90 g/cc, also obtained from the Exxon Chemical Americas.
  • PEB1 KT-221PTM propylene/ethylene/butene random copolymer from Montel Polyolefins USA.
  • PEB2 KT-021PTM propylene/ethylene/butene random copolymer from Montel Polyolefins USA.
  • AB1 Zeeospheres W-410TM ceramic microspheres, used as antiblocking agent with spherical shape and average size (diameter) of 4 micrometers from Zeelan Industries.
  • AB3 Syloblock S200TM used as antiblocking agent with average size (diameter) of 2 micrometers, from W. R. Grace.
  • ABB KAOPOLITE SFO SPECIAL TM blend of kaolin silica having an average particle size of 0.7 microns with approximately 4% by weight of fatty acid amides, obtained from Kaopolite, Inc., of Union, N.J.
  • FA2 KEMAMIDE E Ultra TM fatty amide of erucic acid, obtained from the Witco Corp., Humko Chemical Division, of Charlotte, N.C.
  • MO KAYDOL TM white mineral oil, also supplied by Witco Corp.
  • LLDPE DOWLEX 2045.03 TM linear low density polyethylene, a heterogeneous ethylene/octene copolymer having a density of 0.920 g/cc and a melt index of 1.1, obtained from The Dow Chemical Company, of Midland, Mich.
  • PE1 DowlexTM 2045.04 LLDPE, an ethylene/1-octene copolymer with a density of 0.920 gm/cc and an octene-1 comonomer content of 6.5%.
  • PE2 DowlexTM 2037 LMDPE, an ethylene/1-octene copolymer with a density of 0.935 gm/cc. and an octene-1 comonomer content of 2.5%.
  • EV1 PE 1335 ethylene/vinyl acetate copolymer with 3.3% vinyl acetate monomer, from Rexene.
  • MBC masterbatch of approximately 90% by weight of PP, approximately 4% by weight of ABB, and approximately 6% by weight of a blend of fatty acid amides. (“MB” means masterbatch.)
  • the film was coextruded.
  • the film was made with silicone oil (i.e., polydimethylsiloxane) sprayed onto the inside surface of the tape, immediately after extrusion.
  • silicone oil i.e., polydimethylsiloxane
  • the film structure was oriented 5 ⁇ in the machine direction, and 5 ⁇ in the transverse direction, using a hot air trapped bubble method.
  • the final oriented film had a thickness of about 0.6 mils.
  • a film having the following A/B/C/B/A structure and percent layer thicknesses (10/15/50/15/10) was coextruded:
  • a monolayer film having the following structure was extruded: 90% PEB1+10% MB [94% PEB2+4% kaolin clay+0.5% erucamide+0.5% behemamide+1% oleamide].
  • a film having the same structure as that of Example 3 was made, but which was extruded (see below) such that the layer having the formulation:
  • Vanguard F-100TM from Okura, is believed to be a monolayer polyolefinic film.
  • a film like that of Comparative Example 6 is made, but which includes in the core layer (i.e. the central layer of the film) an antiblocking agent.
  • a film like that of Comparative Example 7 is made, but which includes in the core layer (i.e. the central layer of the film) an antiblocking agent.
  • An fatty acid amide can optionally be present in any of the film layers of films of the present invention, and/or on an outside surface layer of the film.
  • a polyorganosiloxane can optionally be present in any of the film layers of films of the present invention, and/or on an outside surface layer of the film.
  • a mineral oil can optionally be present in any of the film layers of films of the present invention, and/or on an outside surface layer of the film.
  • An antistatic agent can optionally be present in any of the film layers of films of the present invention, and/or on an outside surface layer of the film.
  • An antifogging agent can optionally be present in any of the film layers of films of the present invention, and/or on an outside surface layer of the film.

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US08/706,993 US6210764B1 (en) 1996-08-29 1996-08-29 Film with substrate layer containing antiblocking agent
CA002213362A CA2213362A1 (en) 1996-08-29 1997-08-18 Film with substrate layer containing antiblocking agent
DE69708417T DE69708417T2 (de) 1996-08-29 1997-08-28 Film mit einer Trägerschicht die ein Antiblockmittel enthält
PT97306599T PT826491E (pt) 1996-08-29 1997-08-28 Filme com uma camada de substrato contendo um agente antiaderencia
ES97306599T ES2166050T3 (es) 1996-08-29 1997-08-28 Pelicula con una capa de substrato que contiene agente antibloqueador.
AT97306599T ATE209104T1 (de) 1996-08-29 1997-08-28 Film mit einer trägerschicht die ein antiblockmittel enthält
BR9704559A BR9704559A (pt) 1996-08-29 1997-08-28 Película com camada de substrato contendo agente de antibloqueio
EP97306599A EP0826491B1 (en) 1996-08-29 1997-08-28 Film with substrate layer containing antiblocking agent
ARP970103956A AR009359A1 (es) 1996-08-29 1997-08-29 Pelicula de capas multiples con capa sustrato que contiene un agente antibloqueador

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US20060068183A1 (en) * 2004-09-29 2006-03-30 Curwood, Inc. Packaging laminates containing anti-block particles
US20060216501A1 (en) * 2005-03-24 2006-09-28 Solutia, Inc. Polymer interlayers comprising antiblocking layers
US20070020472A1 (en) * 2005-07-21 2007-01-25 Mills Charles D Composition and method for the addition of saturated slip agents to multilayer polyethylene films
US20070248810A1 (en) * 2006-04-25 2007-10-25 Mcgee Dennis E Coated polymeric film
US7700707B2 (en) 2002-10-15 2010-04-20 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions and articles made therefrom
US20100151218A1 (en) * 2008-05-28 2010-06-17 Curie Kevin J Innerliner with nylon skin layer
US20100297438A1 (en) * 2009-05-21 2010-11-25 Ross Allen W Polymer film comprising roughening material
US20100316843A1 (en) * 2009-05-21 2010-12-16 Lih-Long Chu Polymer film comprising roughening material
US8071687B2 (en) 2002-10-15 2011-12-06 Exxonmobil Chemical Patents Inc. Multiple catalyst system for olefin polymerization and polymers produced therefrom
US8236774B2 (en) 1997-04-18 2012-08-07 Geron Corporation Human telomerase catalytic subunit
US20130034716A1 (en) * 2010-04-14 2013-02-07 Arkema France Impervious breathable ethylene copolymer film
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KR20010020564A (ko) * 1997-06-30 2001-03-15 크라이오백 인코포레이티드 안개서림-내성 포장 필름
US6706389B1 (en) 1997-06-30 2004-03-16 Cryovac, Inc. Fog-resistant packaging film
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PT826491E (pt) 2002-05-31
EP0826491B1 (en) 2001-11-21
ATE209104T1 (de) 2001-12-15
AR009359A1 (es) 2000-04-12
EP0826491A3 (en) 2000-04-12
DE69708417T2 (de) 2002-07-18
ES2166050T3 (es) 2002-04-01
BR9704559A (pt) 1998-12-22
CA2213362A1 (en) 1998-02-28
EP0826491A2 (en) 1998-03-04

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